CN105860133A - Carbon tube masterbatch and application thereof to tire treads - Google Patents

Carbon tube masterbatch and application thereof to tire treads Download PDF

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Publication number
CN105860133A
CN105860133A CN201610464126.3A CN201610464126A CN105860133A CN 105860133 A CN105860133 A CN 105860133A CN 201610464126 A CN201610464126 A CN 201610464126A CN 105860133 A CN105860133 A CN 105860133A
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China
Prior art keywords
carbon
carbon tube
rubber
polymer
mother material
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Granted
Application number
CN201610464126.3A
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Chinese (zh)
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CN105860133B (en
Inventor
徐俊士
谢青
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Xinjiang Wheeler Carbon Neutrality Industrial Park Co., Ltd.
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Shanghai Lvren New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2307/00—Characterised by the use of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2421/00—Characterised by the use of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention relates to a carbon tube masterbatch and an application thereof to tire treads. The carbon tube masterbatch is prepared through the following steps: firstly adding carbon nanotubes to a polymer melt and stirring the carbon nanotubes to form carbon nanotube slurry, then injecting the carbon nanotube slurry into a grinding device with double line contact ceramic grinding tables by a feed pump to be ground, uniformly dispersing the carbon nanotubes in the polymer as the two ceramic grinding tables rotate oppositely, cutting off the carbon nanotubes under the actions of mechanical friction and the interlaminar shear force in the polymer melt and removing the polymer, thus obtaining short carbon nanotubes; and mixing rubber masterbatch, carbon black and the short carbon nanotubes together and carrying out internal mixing processing on the mixture in an internal mixer, thus obtaining the carbon tube masterbatch. The carbon tube masterbatch provided by the invention is applicable to the tire treads and has the effects of not only reducing the production cost of tires but also improving the wear resistance of the tires.

Description

Carbon tube mother material and in the application of tire tread
Technical field
The invention belongs to tire tread technical field of modification, be specifically related to a kind of carbon tube mother material and at tire tread In application.
Background technology
CNT has the mechanical property of excellence, conduction, heat conductivility, thus is considered as that polymer base is multiple The strengthening of condensation material preferable mechanics and function modified material, the composite material exhibits using CNT to make goes out good Good intensity, elasticity and fatigue resistance, CNT also begins to be gradually available in the industry such as rubber tyre, plastics.
But, CNT is nanometer fibrous, self easily reunites and tangles, and carbon nano tube surface is rule Whole graphite wafer structure, surface inertness is big, poor with polymeric matrix affinity, causes CNT at rubber Bad dispersibility in substrate, and cost is the highest, and these limit CNT scale in tire tread Application.
Therefore, existing for CNT application process in tire tread and further optimize demand, this is also It is one of the study hotspot in this technical field and emphasis, the present invention is accomplished especially power and starting point institute ?.
Summary of the invention
For the above-mentioned technical problem overcoming prior art to exist, the present inventor is carrying out substantial amounts of further investigation Afterwards, thus provide a kind of carbon tube mother material and the application in tire tread thereof, not only increase the property of tire Can, and also reduce the production cost of tire.
First aspect, be the present invention relates to a kind of carbon tube mother material, is prepared by following steps:
Step one, first is added in polymer melt stir into carbon nano tube paste, then by material by CNT Infusion enters in the lapping device of the double ceramic millstone of band Line Contacts grinds, and two ceramic millstones turn on the contrary, speed Control 4500～5000rpm, make CNT evenly spread in described polymer, at mechanical friction and Under shearing strength between layers effect in polymer melt, CNT is blocked, remove described polymer, obtain length For 50nm～the short carbon nanometer tube of 5 μm；
Step 2, short carbon nanometer tube rubber master batches, white carbon black, step one obtained is admixed together, in banburying Banburying processing is carried out, it is thus achieved that carbon tube mother material in machine.
Preferably, in step one, this scope of speed 4500～5000rpm of two ceramic millstones includes Belong to any concrete point value therein, such as 4500rpm, 4600rpm, 4700rpm, 4800rpm, 4900rpm, 5000rpm, most preferably 4800rpm, also include what any two point value in these concrete point values was constituted Scope, more preferably 4600～4900rpm.
Preferably, in step one, described polymer is rubber.
Second aspect, the invention still further relates to the application at tire tread of a kind of above-mentioned carbon tube mother material, including following step Rapid: described carbon tube mother material, natural rubber, butadiene rubber, vulcanized rubber powder, Zn0, sulfur, sulfuration are promoted Agent is admixed together, carries out mixed refining process, it is thus achieved that tread rubber sizing material in banbury, then by the tire after mixing Face glue sizing material puts into extruding machine and through mould molding, it is thus achieved that tire tread components.
Compared with prior art, beneficial effects of the present invention is as follows: the present invention is by improving CNT processing work Process, the problem successfully solving CNT bad dispersibility in rubber mass, have developed high property Energy, the carbon tube mother material rubber composite of high intensity, be applied to green energy conservation by carbon tube mother material composite simultaneously In the tread rubber application of tire, carbon tube mother material composite reduces tire drag and improves braking distance (fuel-economizing 5% can be realized to than conventional white carbon black tire), and have fine antistatic property, simultaneous wheels is viviparous Produce cost and reduce 8%, wear-resisting improve 30%, it is achieved that CNT application in tire tread glue, can As produce high-performance energy-saving wear-resistant tire tread new material, on Tire production application time have simple process, Production efficiency is high, without changing the advantage of existing former, beneficially high-performance energy-saving wear-resistant tire is looked unfamiliar Popularization in product method tire enterprise at home.
Accompanying drawing explanation
Fig. 1 is the scattered schematic diagram of the CNT in the present invention.
Fig. 2 is the preparation of the carbon tube mother material in the present invention and at the process chart of tire tread applications.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in this area Technical staff is further appreciated by the present invention, but limits the present invention the most in any form.It should be pointed out that, to this For the those of ordinary skill in field, without departing from the inventive concept of the premise, it is also possible to make some deformation And improvement.These broadly fall into protection scope of the present invention.
The preparation of embodiment 1-4 carbon tube mother material and the application in tire tread thereof
Step one, the dispersion (as shown in Figure 1) of CNT: first described CNT is added to rubber polymerization Thing melt stirs into carbon nano tube paste, is then entered the grinding of the double ceramic millstone of band Line Contacts by material infusion Grinding in device, two ceramic millstones turn on the contrary, and speed controlling, at 4800rpm, makes CNT uniform It is distributed in polymer, by CNT under the shearing strength between layers effect in mechanical friction and polymer melt Block, remove polymer, obtain a length of 50nm～the short carbon nanometer tube of 5 μm；
Step 2, obtains rubber master batches (composition is rubber), white carbon black (employing cracking black carbon), step one Short carbon nanometer tube is admixed together, carries out banburying processing, it is thus achieved that carbon tube mother material in banbury；
Step 3, carbon tube mother material, natural rubber, butadiene rubber, vulcanized rubber powder, Zn0, sulfur, sulfuration Accelerator is admixed together, carries out mixed refining process, it is thus achieved that tread rubber sizing material in banbury, then by after mixing Tread rubber sizing material put into extruding machine through mould molding, it is thus achieved that tire tread components, process chart As shown in Figure 2.
Composition of raw materials (the weight portion g) that table 1 embodiment 1-4 uses
Title material Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Natural rubber 80 80 80 80
Butadiene rubber 20 20 20 20
Zinc oxide 1.5 1.5 1.5 1.5
White carbon black 50 50 50 50
Carbon tube mother material 10 15
Sulfur 2 2 2 2
Accelerator 1.5 1.5 1.5 1.5
Amount to 155 155 165 170
The performance test results of the tire tread parts that table 2 embodiment 1-4 obtains
Adding after short carbon nanometer tube, the processing characteristics of elastomeric compound has had and has been obviously improved, the hardness of vulcanizate, resilience Rate, hot strength and tearing strength are all improved, and resistance to rolling reduces；Tire high speed performance is better than not adding The reference tire of short carbon nanometer tube, by testing adding short carbon nanometer tube tread rubber heat transfer coefficient, at 60 degree and Under the situation of 80 degree, heat transfer coefficient improves 25%.Crown surface temperature and groove bottom temperature in road test Reducing, tire wear improves 30%, extends the service life of tire, and cost also reduces than regular convention formula About 8%.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in Above-mentioned particular implementation, those skilled in the art can make various deformation within the scope of the claims or repair Changing, this has no effect on the flesh and blood of the present invention.

Claims (4)

1. a carbon tube mother material, it is characterised in that prepared by following steps:
Step one, first is added in polymer melt stir into carbon nano tube paste, then by material by CNT Infusion enters in the lapping device of the double ceramic millstone of band Line Contacts grinds, and two ceramic millstones turn on the contrary, speed Control 4500～5000rpm, make CNT evenly spread in described polymer, at mechanical friction and Under shearing strength between layers effect in polymer melt, CNT is blocked, remove described polymer, obtain length For 50nm～the short carbon nanometer tube of 5 μm；
Step 2, short carbon nanometer tube rubber master batches, white carbon black, step one obtained is admixed together, in banburying Banburying processing is carried out, it is thus achieved that carbon tube mother material in machine.
2. carbon tube mother material as claimed in claim 1, it is characterised in that in step one, two ceramic millstones Speed controlling at 4800rpm.
3. carbon tube mother material as claimed in claim 1, it is characterised in that in step one, described polymer is Rubber.
4. carbon tube mother material described in any one of claim 1-3 is in the application of tire tread, it is characterised in that include Following steps: by described carbon tube mother material, natural rubber, butadiene rubber, vulcanized rubber powder, Zn0, sulfur, sulfur Change accelerator admixed together, in banbury, carry out mixed refining process, it is thus achieved that tread rubber sizing material, then by mixing After tread rubber sizing material put into extruding machine through mould molding, it is thus achieved that tire tread parts.
CN201610464126.3A 2016-06-23 2016-06-23 Carbon tube mother material and its application in tire tread Active CN105860133B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928518A (en) * 2017-04-20 2017-07-07 山东宝力科技有限公司 CNT composite high-performance tire tread rubber and its application
CN107746477A (en) * 2017-09-01 2018-03-02 上海绿人生态经济环境保护研究所 A kind of manufacture method of carbon nanometer tire tread containing all-steel cord and products thereof
CN108250497A (en) * 2016-12-28 2018-07-06 山东吉路尔轮胎有限公司 The preparation method of carbon nanotube tire and high abrasion high grip carbon nanotube tire
WO2019139623A1 (en) * 2018-01-12 2019-07-18 Compagnie Generale Des Etablissements Michelin Rubber compositions with dissaggregated carbon nanotubes
CN110643080A (en) * 2019-09-04 2020-01-03 芜湖集拓实心胎有限公司 Low themogenesis engineering solid tire
CN110678508A (en) * 2017-05-15 2020-01-10 大陆轮胎德国有限公司 Sulfur-crosslinked rubber mixture containing Carbon Nanotubes (CNTs) for vehicle tires, vehicle tire with sulfur-crosslinked rubber mixture, and method for producing sulfur-crosslinked rubber mixture containing carbon nanotubes
CN111333060A (en) * 2020-04-23 2020-06-26 上海轮匠科技有限公司 Wet compounding method of graphene oxide/carbon nano tube and carbon nano carbon black
CN115028906A (en) * 2022-05-09 2022-09-09 青岛黑猫新材料研究院有限公司 Preparation method of high-dispersion carbon nano composite masterbatch

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CN101607224A (en) * 2009-07-13 2009-12-23 刘晋荣 A kind of method that improves efficiency in truncating carbon nano-tubes by mechanical grinding
CN102702591A (en) * 2012-06-25 2012-10-03 青岛科技大学 Hydrogenated nitrile rubber/carbon nanotube composite material and preparation method thereof
CN103694505A (en) * 2013-12-24 2014-04-02 苏州华东橡胶工业有限公司 Compound carbon nanotube and rubber material and preparation method thereof
CN105459284A (en) * 2014-08-25 2016-04-06 山东大展纳米材料有限公司 Liquid phase continuous mixing process of high dispersion carbon nanotube masterbatch and rubber product thereof

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Publication number Priority date Publication date Assignee Title
CN101607224A (en) * 2009-07-13 2009-12-23 刘晋荣 A kind of method that improves efficiency in truncating carbon nano-tubes by mechanical grinding
CN102702591A (en) * 2012-06-25 2012-10-03 青岛科技大学 Hydrogenated nitrile rubber/carbon nanotube composite material and preparation method thereof
CN103694505A (en) * 2013-12-24 2014-04-02 苏州华东橡胶工业有限公司 Compound carbon nanotube and rubber material and preparation method thereof
CN105459284A (en) * 2014-08-25 2016-04-06 山东大展纳米材料有限公司 Liquid phase continuous mixing process of high dispersion carbon nanotube masterbatch and rubber product thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250497A (en) * 2016-12-28 2018-07-06 山东吉路尔轮胎有限公司 The preparation method of carbon nanotube tire and high abrasion high grip carbon nanotube tire
CN106928518B (en) * 2017-04-20 2018-03-23 山东宝力科技有限公司 CNT composite high-performance tire tread rubber and its application
CN106928518A (en) * 2017-04-20 2017-07-07 山东宝力科技有限公司 CNT composite high-performance tire tread rubber and its application
CN110678508A (en) * 2017-05-15 2020-01-10 大陆轮胎德国有限公司 Sulfur-crosslinked rubber mixture containing Carbon Nanotubes (CNTs) for vehicle tires, vehicle tire with sulfur-crosslinked rubber mixture, and method for producing sulfur-crosslinked rubber mixture containing carbon nanotubes
US11326028B2 (en) 2017-05-15 2022-05-10 Continental Reifen Deutschland Gmbh Sulfur-crosslinked rubber mixture for vehicle tires, containing carbon nanotubes (CNT), vehicle tire having the sulfur-crosslinked rubber mixture, and method for producing the sulfur-crosslinked rubber mixture containing carbon nanotubes
CN107746477A (en) * 2017-09-01 2018-03-02 上海绿人生态经济环境保护研究所 A kind of manufacture method of carbon nanometer tire tread containing all-steel cord and products thereof
CN111836731A (en) * 2018-01-12 2020-10-27 米其林集团总公司 Rubber composition with depolymerized carbon nanotubes
WO2019140369A1 (en) * 2018-01-12 2019-07-18 Compagnie Generale Des Etablissements Michelin Rubber compositions with dissaggregated carbon nanotubes
WO2019140396A1 (en) * 2018-01-12 2019-07-18 Compagnie Generale Des Etablissements Michelin Rubber compositions with disaggregated carbon nanotubes
CN111727124A (en) * 2018-01-12 2020-09-29 米其林集团总公司 Method for producing rubber composition using depolymerized carbon nanotubes
WO2019140393A1 (en) * 2018-01-12 2019-07-18 Compagnie Generale Des Etablissements Michelin Method for producing rubber compositions with disaggregated carbon nanotubes
WO2019139623A1 (en) * 2018-01-12 2019-07-18 Compagnie Generale Des Etablissements Michelin Rubber compositions with dissaggregated carbon nanotubes
US11697728B2 (en) 2018-01-12 2023-07-11 Compagnie Generale Des Etablissements Michelin Rubber compositions with dissagregated carbon nanotubes
CN111727124B (en) * 2018-01-12 2023-09-29 米其林集团总公司 Method for producing rubber composition using depolymerized carbon nanotubes
US11814523B2 (en) 2018-01-12 2023-11-14 Compagnie Generale Des Etablissements Michelin Method for producing rubber compositions with disaggregated carbon nanotubes
CN110643080A (en) * 2019-09-04 2020-01-03 芜湖集拓实心胎有限公司 Low themogenesis engineering solid tire
CN111333060A (en) * 2020-04-23 2020-06-26 上海轮匠科技有限公司 Wet compounding method of graphene oxide/carbon nano tube and carbon nano carbon black
CN115028906A (en) * 2022-05-09 2022-09-09 青岛黑猫新材料研究院有限公司 Preparation method of high-dispersion carbon nano composite masterbatch

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